Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 22
Filtrar
Mais filtros








Base de dados
Assunto principal
Intervalo de ano de publicação
1.
J Phys Chem B ; 128(18): 4504-4512, 2024 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-38683052

RESUMO

In electrolytes, the self- and interdiffusion coefficients, transport numbers, and electrical conductivity can be used to determine velocity cross-correlation coefficients (VCC) that are also accessible through molecular dynamics simulations. In an ionic liquid or molten salt, there are only three, corresponding to correlations between the velocities of distinct ion pairs (cation-anion, cation-cation, and anion-anion) averaged over both the ensemble and time, calculable from experimental ion self-diffusion coefficients and the electrolyte conductivity. Most usually, the mass-fixed frame of reference (with velocities relative to that of the center of mass of the system) is used to discuss the VCC and the distinct diffusion coefficients (DDC) derived from them. Recent work in the literature has suggested a dependence of the DDC on the ratio of the anion to cation mass. Here, we demonstrate, using our own and literature transport property data for a large number of ionic liquids and molten salts, that the trends observed depend on the particular choice of velocity reference frame, mass-, number-, or volume-fixed. The perception of ion-ion interactions may be distorted in the mass- and volume fixed frames when the co-ions have very different masses or volumes, particularly for systems containing light lithium ions.

2.
ACS Omega ; 7(46): 42155-42162, 2022 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-36440108

RESUMO

This paper reports a series of liquid materials suitable for use as high-performance separation membranes in direct air capture. Upon mixing two ionic liquids (ILs), namely N-(2-aminoethyl)ethanolamine-based IL ([AEEA][X]) and 1-ethyl-3-methylimidazolium acetate ([emim][AcO]), the resulting mixtures with a specific range of their composition showed higher CO2 absorption rates, larger CO2 solubilities, and lower absolute enthalpies of CO2 absorption compared to those of single ILs. NMR spectroscopy of the IL mixture after exposure to 13CO2 allowed elucidation of the chemisorbed species, wherein [AEEA][X] reacts with CO2 to form CO2-[AEEA]+ complexes stabilized by hydrogen bonding with acetate anions. Supported IL membranes composed of [AEEA][X]/[emim][AcO] mixtures were then fabricated, and the membrane with a suitable mixing ratio showed a CO2 permeability of 25,983 Barrer and a CO2/N2 selectivity of 10,059 at 313.2 K and an applied CO2 partial pressure of 40 Pa without water vapor. These values are higher than those reported for known facilitated transport membranes.

3.
Phys Chem Chem Phys ; 24(23): 14430-14439, 2022 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-35649435

RESUMO

New high-pressure self-diffusion data are reported for the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIM][Tf2N]) at pressures up to 363 MPa in the temperature range 288-348 K. The cation and anion activation volumes derived from these are found to be equal at a fixed temperature, within experimental error, in contradiction to a report in the literature that they differ significantly. Self-diffusion activation volumes derived from our earlier high-pressure diffusion studies also show equality for the respective cations and anions of bis(trifluoromethylsulfonyl)amide, tetrafluoroborate and hexafluorophosphate salts with various cations. Stokes-Einstein-Sutherland analysis and density scaling are applied to the [EMIM][Tf2N] self-diffusion measurements and support the conclusion that pressure effects both cation and anion mass (and hence charge) transport in the same way. The density scaling parameters are consistent with the theoretical predictions of Knudsen et al. and agree with that for the viscosity, as for other ionic liquids.

4.
Phys Chem Chem Phys ; 23(37): 21350, 2021 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-34524314

RESUMO

Correction for 'Self-diffusion, velocity cross-correlation, distinct diffusion and resistance coefficients of the ionic liquid [BMIM][Tf2N] at high pressure' by Kenneth R. Harris et al., Phys. Chem. Chem. Phys., 2015, 17, 23977-23993, DOI: 10.1039/C5CP04277A.

5.
Phys Chem Chem Phys ; 19(16): 10527-10542, 2017 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-28393945

RESUMO

Transport properties are examined in some detail for samples of the low temperature molten salt N-propyl-N-methyl pyrrolidinium bis(fluorosulfonyl)imide [Pyr13][FSI] from two different commercial suppliers. A similar set of data is presented for two different concentrations of binary lithium-[Pyr13][FSI] salt mixtures from one supplier. A new and significantly different production process is used for the synthesis of Li[FSI] as well as the [Pyr13]+ salt used in the mixtures. Results for the viscosity, conductivity, and self-diffusion coefficients, together with the density and expansivity and apparent molar volume, are reported over the temperature range of (0 to 80) °C. The data for neat [Pyr13][FSI] are discussed in the context of velocity cross correlation (VCC or fij) and Laity resistance (rij) coefficients. Unusually, f+- ∼ f++ < f--. The three resistance coefficients are of similar magnitude indicating all three ion-ion interactions contribute to the transport properties, not just the cation-anion interaction. The composition dependence of the transport properties is compared to previously reported data for the same and related compounds: in contrast to high-temperature molten salt mixtures, this is an exponential dependence. The Nernst-Einstein parameter Δ, which contains information on the correlations of the ionic velocities and is determined by differences in the VCC for the various ion-ion combinations, was calculated for both the neat ionic liquid and its binary mixture. It increases with increasing lithium concentration. The new data set also allows some conclusions with regards to the lithium-[FSI]- coordination environment.

6.
J Phys Chem B ; 121(13): 2873-2881, 2017 04 06.
Artigo em Inglês | MEDLINE | ID: mdl-28263064

RESUMO

Interactions of 1-butyl-3-methylimidazolium cation ([C4mim]+) with bis(trifluoromethanesulfonyl)amide anion ([TFSA]-) and diethyleneglycol dimethyl ether (diglyme) in mixtures of [C4mim][TFSA] ionic liquid and diglyme have been investigated using 1H and 13C NMR spectroscopy and molecular dynamics (MD) simulations. The results of NMR chemical shift measurements and MD simulations showed that the diglyme oxygen atoms have contact with the imidazolium hydrogen atoms of [C4mim]+ in the mixtures. The contact between the hydrogen atoms of imidazolium and the oxygen atoms of [TFSA]- remains even when the diglyme mole fraction (xdiglyme) increases up to 0.9. However, the coordination numbers of the hydrogen atoms of [C4mim]+ with oxygen atoms of diglyme increase with xdiglyme. The [TFSA]- anions around [C4mim]+ are not completely replaced by diglyme even at xdiglyme > 0.9. The MD simulations revealed that the diglymes also have contact with the butyl group of [C4mim]+. The methyl groups of diglyme prefer to have contact with the terminal methyl group of the butyl group, whereas the diglyme oxygen atoms prefer to have contact with the methylene group connected to the imidazolium ring of [C4mim]+.

7.
J Phys Chem B ; 120(50): 12937-12949, 2016 12 22.
Artigo em Inglês | MEDLINE | ID: mdl-27959564

RESUMO

Earlier measurements of the self-diffusion coefficients of 1-alkyl-3-methylimidazolium (or [RMIM], R = alkyl) tetrafluoroborates and hexafluorophosphates have been revised and extended to 90 °C. The main changes are to DS+ and DS- for [HMIM][PF6] ([C6C1Im][PF6]) and DS- for [OMIM][BF4] ([C8C1Im][BF4]). New atmospheric pressure self-diffusion, density, and conductivity data are provided for [HMIM][BF4] ([C6C1Im][BF4]). Velocity cross-correlation, distinct diffusion, and Laity resistance coefficients have been calculated. There is no evidence for ion association. A new relation between the Nernst-Einstein deviation parameter (Δ) and resistance coefficients (rij) is derived; Δ tends toward 0.5 when the like-ion rii are much smaller than the unlike-ion rij, i.e., when the counterion interactions dominate. [OMIM]+ ion salts approach this limit. Stokes-Einstein-Sutherland and Walden plots overlap almost quantitatively for [BF4]-, [PF6]-, and Cl- salts with a common [RMIM]+ cation. That is, in thermodynamic states that have the same viscosity, the salt molar conductivities and hence ionic electrical mobilities of, say, [BMIM][BF4] and [BMIM][PF6] are almost equal, as are the corresponding Brownian or diffusive mobilities, (DSi/RT), for the cation, and also for these three small anions.

9.
Phys Chem Chem Phys ; 17(37): 23977-93, 2015 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-26313817

RESUMO

Ion self-diffusion coefficients (DSi) have been measured for the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide [BMIM][Tf2N] at pressures to 200 MPa between 25 and 75 °C and at 0.1 MPa between 10 and 90 °C. Self-diffusion coefficients are reported for 1-ethyl-, 1-hexyl- and 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide salts at 0.1 MPa, supplemented by viscosity, electrical conductivity and density measurements. Velocity cross-correlation (VCC, fij) and distinct diffusion coefficients (D) are calculated from the data. Both DSi and D are analysed in terms of (fractional) Stokes-Einstein-Sutherland (SES) equations. SES and Walden plots show almost identical slopes, with high-pressure isotherms and the atmospheric pressure isobar falling on common, single lines for each property for [BMIM][Tf2N]. SES plots for the anion self-diffusion coefficients for the [RMIM][Tf2N] (R = alkyl) series are coincident, whereas those for the cations depend on their alkyl substitution, as do the Walden plots. In common with other [Tf2N](-) salts, the VCC follow the order f-- < f++ < f+-. The Nernst-Einstein deviation parameter Δ for [BMIM][Tf2N] is independent of temperature and pressure. Those for the other [Tf2N](-) salts are independent of temperature. Δ increases in magnitude with increasing alkyl chain length on the cation. The transport properties of [BMIM][Tf2N] are re-examined in terms of density scaling using reduced conductivities and reduced molar conductivities for the first time. Identical scaling parameters (γ) are obtained for the several reduced transport properties. This result is supported by data for other ionic liquids. It is suggested that the γ for ionic liquids may depend on packing fraction.

10.
Phys Chem Chem Phys ; 16(19): 9161-70, 2014 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-24709921

RESUMO

Ion self-diffusion coefficients have been measured for ionic liquids based on the cations N-acetoxyethyl-N,N-dimethyl-N-ethylammonium ([N(112,2OCO1)](+)) and its non-functionalised analogue, N,N-dimethyl-N-ethyl-N-pentylammonium ([N1125](+)), and N,N-dimethyl-N-ethyl-N-methoxyethoxyethylammonium ([N(112,2O2O1)](+)), and its analogue, N,N-dimethyl-N-ethyl-N-heptylammonium ([N1127](+)) and the bis(trifluoromethanesulfonyl)amide anion. The functionalised chain on an ammonium cation has the same length, in terms of the number of atoms, as the non-functionalised chain of the corresponding analogue. For [N(112,2OCO1)][Tf2N] and [N1127][Tf2N], the cation and anion self-diffusion coefficients are equal, within experimental error, whereas for [N1125][Tf2N], the cation diffuses more quickly, and for [N(112,2O2O1)][Tf2N], it is the anion that diffuses more quickly than the ether-functionalised cation. But these differences are relatively small, just beyond experimental error. The data are used to calculate velocity cross-correlation coefficients (VCC or f(ij)) and distinct diffusion coefficients (D(ij)(d)). Both the self-diffusion and distinct diffusion coefficients are analysed in terms of (fractional) Stokes-Einstein-Sutherland equations. Though the self-diffusion coefficients, as with the conductivity and viscosity, show marked differences in absolute terms between the functionalised and non-functionalised forms, being higher for the ethoxy-substituted IL and lower for the acetoxy-substituted IL, these are largely removed by scaling with the viscosity. Thus the transport properties are better understood as functions of the viscosity rather than the temperature and density, per se. The presence of the alkoxy-substituted side chains is known to change the local mesoscopic liquid structure, but it appears once this is done, the transport properties scale correspondingly. In the case of the acetoxy-substituted IL, this is also largely the case, but the Nernst-Einstein deviation parameter, Δ, which depends on the difference between the anion-cation VCC and the mean of the cation-cation and anion-anion VCCs, is smaller than that of its analogue salt, and also temperature dependent.

11.
Chemistry ; 19(52): 17733-44, 2013 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-24288151

RESUMO

Two N-donor-functionalised ionic liquids (ILs), 1-ethyl-1,4-dimethylpiperazinium bis(trifluoromethylsulfonyl)amide (1) and 1-(2-dimethylaminoethyl)-dimethylethylammonium bis(trifluoromethylsulfonyl)amide (2), were synthesised and their electrochemical and transport properties measured. The data were compared with the benchmark system, N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (3). Marked differences in thermal and electrochemical stability were observed between the two tertiary-amine-functionalised salts and the non-functionalised benchmark. The former are up to 170 K and 2 V less stable than the structural counterpart lacking a tertiary amine function. The ion self-diffusion coefficients (Di ) and molar conductivities (Λ) are higher for the IL with an open-chain cation (2) than that with a cyclic cation (1), but less than that with a non-functionalised, heterocyclic cation (3). The viscosities (η) show the opposite behaviour. The Walden [Λ[proportionality](1/η)(t) ] and Stokes-Einstein [Di /T)[proportionality](1/η)(t) ] exponents, t, are very similar for the three salts, 0.93-0.98 (±0.05); that is, the self-diffusion coefficients and conductivity are set by η. The Di for 1 and 2 are the same, within experimental error, at the same viscosity, whereas Λ for 1 is approximately 13% higher than that of 2. The diffusion and molar conductivity data are consistent, with a slope of 0.98±0.05 for a plot of ln(ΛT) against ln(D+ +D- ). The Nernst-Einstein deviation parameters (Δ) are such that the mean of the two like-ion VCCs is greater than that of the unlike ions. The values of Δ are 0.31, 0.36 and 0.42 for 3, 1 and 2, respectively, as is typical for ILs, but there is some subtlety in the ion interactions given 2 has the largest value. The distinct diffusion coefficients (DDC) follow the order D(d)__ < D(d)++ < D(d)+_, as is common for [Tf2N](-) salts. The ion motions are not correlated as in an electrolyte solution: instead, there is greater anti-correlation between the velocities of a given anion and the overall ensemble of anions in comparison to those for the cationic analogue, the anti-correlation for the velocities of which is in turn greater than that for a given ion and the ensemble of oppositely charged ions, an observation that is due to the requirement for the conservation of momentum in the system. The DDC also show fractional SE behaviour with t~0.95.

12.
Faraday Discuss ; 154: 425-38; discussion 439-64, 465-71, 2012.
Artigo em Inglês | MEDLINE | ID: mdl-22455034

RESUMO

High pressure measurements have been made of viscosities, ion self-diffusion coefficients and electrical conductivities of ionic liquids, mainly of imidazolium salts. We review how these properties have been analysed in terms of the empirical Stokes-Einstein, Walden and Nernst-Einstein equations, and examine trends revealed by the phenomenological approach of velocity correlation coefficients and the more general theory of density scaling. Finally we examine the possibility of dynamic crossover in the transport properties of ionic liquids.


Assuntos
Líquidos Iônicos/química , Difusão , Condutividade Elétrica , Pressão , Termodinâmica , Viscosidade
13.
J Phys Chem B ; 115(36): 10622-30, 2011 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-21815618

RESUMO

(27)Al NMR longitudinal relaxation times, T(1,obs)((27)Al), of [Al(acac)(3)] and [Al(hfa)(3)] (Hacac = acetylacetone, Hhfa = hexafluoroacetylacetone) in CH(3)CN and CO(2) were measured over a wide range of temperature and pressure. The rotational correlation times, τ(r), of the tris(ß-diketonato)aluminum(III) complexes were determined from T(1,obs)((27)Al) using (27)Al quadrupole coupling constants, eQq/h((27)Al), which were also obtained to be 3.11 and 3.22 MHz for [Al(acac)(3)] and [Al(hfa)(3)], respectively, in CD(3)CN by the dual spin probe technique in the present study. At each temperature, τ(r) increased almost linearly with increasing viscosity, η, in both CH(3)CN and CO(2); however, τ(r) in CO(2) at near critical densities deviated appreciably upward, as shown in a similar analogue of bis(acetylacetonato)beryllium(II), [Be(acac)(2)] (Umecky; et al. J. Phys. Chem. B 2002, 106, 11114). The η/T dependence of τ(r) was examined to discuss intermolecular interactions between the complexes and solvent molecules in terms of the fluorination and geometrical effects. The degree of solute-solvent interactions increases in the order [Be(acac)(2)] < [Al(hfa)(3)] < [Al(acac)(3)] in CH(3)CN and [Al(acac)(3)] < [Be(acac)(2)] < [Al(hfa)(3)] in CO(2). The results suggest that dipolar CH(3)CN molecules interact with negatively charged oxygen atoms in the complexes, whereas nonpolar CO(2) prefers fluorinated substituents as well as quasi-aromatic rings in the ligands. Moreover, the relationship between the rotational and translational motions of tris(acetylacetonato)metal(III), [M(III)(acac)(3)], in CO(2) was investigated.

14.
J Chem Phys ; 135(24): 244502, 2011 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-22225164

RESUMO

Short- and long-range liquid structures of [C(n)mIm(+)][TFSA(-)] with n = 2, 4, 6, 8, 10, and 12 have been studied by high-energy x-ray diffraction (HEXRD) and small-angle neutron scattering (SANS) experiments with the aid of MD simulations. Observed x-ray structure factor, S(Q), for the ionic liquids with the alkyl-chain length n > 6 exhibited a characteristic peak in the low-Q range of 0.2-0.4 Å(-1), indicating the heterogeneity of their ionic liquids. SANS profiles I(H)(Q) and I(D)(Q) for the normal and the alkyl group deuterated ionic liquids, respectively, showed significant peaks for n = 10 and 12 without no form factor component for large spherical or spheroidal aggregates like micelles in solution. The peaks for n = 10 and 12 evidently disappeared in the difference SANS profiles ΔI(Q) [=I(D)(Q) - I(H)(Q)], although that for n = 12 slightly remained. This suggests that the long-range correlations originated from the alkyl groups hardly contribute to the low-Q peak intensity in SANS. To reveal molecular origin of the low-Q peak, we introduce here a new function; x-ray structure factor intensity at a given Q as a function of r, S(Q) (peak)(r). The S(Q) (peak)(r) function suggests that the observed low-Q peak intensity depending on n is originated from liquid structures at two r-region of 5-8 and 8-15 Å for all ionic liquids examined except for n = 12. Atomistic MD simulations are consistent with the HEXRD and SANS experiments, and then we discussed the relationship between both variations of low-Q peak and real-space structure with lengthening the alkyl group of the C(n)mIm.

15.
J Phys Chem B ; 114(43): 13628-36, 2010 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-20936838

RESUMO

We experimentally determined the density and mole fraction of CO(2) (x(CO(2))) for CO(2)-alcohol (methanol, ethanol, propanol, butanol, isopropyl alcohol, and tert-butyl alcohol) mixtures and performed molecular dynamics (MD) simulations to study the mechanisms of volume expansion at 40 °C. The volume as calculated by vapor-liquid equilibrium (VLE) data increased with decreasing alkyl chain length, although there was no effect of branched alkyl groups. Analysis of the hydrogen bond network showed that the average number of hydrogen bonds per alcohol molecule decreased with increasing branched methyl groups. At pure alcohol condition, large size hydrogen bond networks were made. With further addition of CO(2) molecules, it became difficult to contain the large hydrogen bond networks. Furthermore, the hydrogen bond networks changed to a cyclic pentamer or tetramer, and volume expansion occurred.

16.
Anal Sci ; 24(10): 1373-6, 2008 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-18845904

RESUMO

The liquid structure of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM]PF(6), was investigated by neutron diffraction with H/D substitution method, where the hydrogen atoms in the imidazolium ring were partially deuterated. The local structures around the ring hydrogen atoms in liquid are very similar to those estimated from the crystal structure.

17.
J Phys Chem B ; 112(32): 9830-40, 2008 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-18637684

RESUMO

The self-diffusion coefficients (D) of the cation and anion in the ionic liquids 1-hexyl-3-methylimidazolium and 1-octyl-3-methylimidazolium hexafluorophosphates ([HMIM]PF6 and [OMIM]PF6) and 1-butyl-3-methylimidazolium and 1-octyl-3-methylimidazolium tetrafluoroborates ([BMIM]BF4) and ([OMIM]BF4) have been determined together with the electrical conductivities (kappa) of [HMIM]PF6 and [BMIM]BF4 under high pressure. The pressure effect on the transport coefficients is discussed in terms of velocity cross-correlation coefficients (VCCs or fij), the Nernst-Einstein equation (ionic diffusivity-conductivity), and the fractional form of the Stokes-Einstein relation (viscosity-conductivity and viscosity-diffusivity). The (mass-fixed frame of reference) VCCs for the cation-cation, anion-anion, and cation-anion pairs are all negative and strongly pressure dependent, increasing (becoming less negative) with increasing pressure. VCCs are the more positive for the stronger ion-velocity correlations; therefore, f+ - is least negative in each case. In general, f- - is less negative than f+ +, indicating a smaller correlation of velocities of distinct cations than that for distinct anions. However, for [OMIM]PF6, the like-ion fii are very similar to one another. Plots of the VCCs for a given ion-ion correlation against fluidity (reciprocal viscosity) show the fij to be strongly correlated with the viscosity as either temperature or pressure are varied, that is, fij approximately fij(eta). The Nernst-Einstein deviation parameter, Delta, is nearly constant for each salt under the conditions examined. It is emphasized that nonzero values of Delta are not necessarily due to ion pairing but result from differences between the like-ion and unlike-ion VCCs, because Delta is proportional to (f+ + + f- - - 2 f+ -). The diffusion and molar conductivity (Lambda) data are found to fit fractional forms of the Stokes-Einstein relationship, (LambdaT) proportional, variant (T/eta)(t) and Di proportional, variant (T/eta)(t), with t=(0.90+/-0.05) for all these ionic liquids, independent of both temperature and pressure within the ranges studied.

18.
J Nanosci Nanotechnol ; 8(2): 493-502, 2008 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-18464362

RESUMO

The behavior of oxide film on pure iron passivated in a borate buffer solution and subsequently radiated by infrared light (IR) was investigated in comparing to that by just IR annealing without passivation, and was evaluated by film structure, etc. The effect of thermal annealing over 250 degrees C was observed with gamma-Fe2O3 grain growth and sharp increase in surface roughness, film thickness and oxygen content. An ellipsometric parameter of tan psi was sensitively reflected by annealing effect, and tan psi curve had a shoulder at 150 degrees C for 5 min and a peak of tan psi was shifted from 350 nm to 450 nm in wavelength. This shift was also caused by the formation of gamma-Fe2O3, because the peak was also observed in tan psi of the bulk Fe2O3 family. Passivation effects at 800 mV prior to IR annealing on thickness and oxygen content changed at 150 degrees C, and decreased tan psi at 350 nm and excessive film growth over 250 degrees C, and increased oxygen content under 100 degrees C and surface roughness at 50-250 degrees C. The terrace width with atomic scale flatness was slightly increase by passivation prior to IR annealing at 50-250 degrees C, and the maximum terrace width reached larger than 10 nm by passivation and IR annealing at 100 degrees C for 30 min.

19.
J Phys Chem B ; 111(8): 2062-9, 2007 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-17274650

RESUMO

The self-diffusion coefficients (D) of the cation and anion in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) have been determined together with the electrical conductivity (kappa) under high pressure. All three quantities strongly decrease with increasing pressure to approximately 20% of their atmospheric pressure values at 200 MPa. D(PF6-) is always less than D([BMIM]+), despite the larger van der Waals volume of the cation. The pressure effect on the transport coefficients is discussed in terms of velocity correlation coefficients (VCCs or fij), the Nernst-Einstein equation (ionic diffusivity-conductivity), and the fractional form of the Stokes-Einstein relation (viscosity-conductivity and viscosity-diffusivity). It was found that the VCCs for the cation-cation, anion-anion, and cation-anion pairs are all negative and strongly pressure-dependent, increasing (becoming less negative) with increasing pressure. However, when the values of the VCCs for a given isotherm are normalized relative to the corresponding atmospheric pressure values, they collapse onto a single curve, as might be expected because the pressure should affect the interionic velocity correlations in the same way for each type of interaction. These isothermal curves can be represented by the form exp(alphap + betap2). The Nernst-Einstein deviation parameter, Delta, which depends on the differences between the like-like ion and unlike ion VCCs (f++ + f-- - 2f+-), is very nearly constant under the conditions examined. The diffusion and molar conductivity (Lambda) data are found to fit fractional forms of the Stokes-Einstein relationship with the viscosity, (LambdaT) proportional, variant (T/eta)t and Di proportional, variant (T/eta)t , with t = (0.92 +/- 0.05), independent of both temperature and pressure within the ranges studied and common to the three independently determined properties.

20.
Chem Commun (Camb) ; (17): 1828-30, 2006 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-16622497

RESUMO

A new physical method was proposed to control the liquid properties of room temperature ionic liquids (RT-ILs) in combination with nanoporous materials; the melting point of ILs confined in nanopores remarkably decreases in proportion to the inverse of the pore size.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA